The present invention describes a catalyst system comprising metallocene, cocatalyst, support material and, if desired, further organometallic compounds. The catalyst system can advantageously be used for the polymerization of olefins, where the use of aluminoxanes such as methylaluminoxane (MAO), which usually has to be used in a large excess, as cocatalyst can be dispensed with and a high catalyst activity and good polymer morphology are nevertheless achieved.
The role of cationic complexes in Ziegler-Natta polymerization using metallocenes is generally recognized (H. H. Brintzinger, D. Fischer, R. Mxc3xclhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107,1255-1283).
The preparation of such cationic alkyl complexes opens up the possibility of obtaining MAO-free catalysts having comparable activity; in this case the cocatalyst can be used in a virtually stoichiometric amount.
The synthesis of xe2x80x9ccation-likexe2x80x9d metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, Volume 113, page 3623.
A process for preparing salts of the formula LMX+ XAxe2x88x92 by the above-described principle is claimed in EP-A-0,520,732.
EP-A-0,558,158 describes zwitterionic catalyst systems which are prepared from dialkylmetallocene compounds and salts of the formula [R3NH]+][B(C6H5)4]xe2x88x92. The reaction of such a salt with, for example, CP2ZrMe2 gives, as a result of protolysis with elimination of methane, a methylzirconocene cation as intermediate. This reacts further via Cxe2x80x94H activation to give the zwitterion Cp2Zr+-(m-C6H4)-BPh3xe2x88x92. Here, the Zr atom is covalently bound to a carbon atom of the phenyl ring and is stabilized by means of agostic hydrogen bonds. U.S. Pat. No. 5,348,299 describes zwitterionic catalyst systems which are prepared from dialkylmetallocene compounds and salts of the formula [R3NH]+[B(C6F5)4]xe2x88x92 by protolysis. The Cxe2x80x94H activation as subsequent reaction does not occur here.
EP-A-0,426,637 utilizes a process in which the Lewis-acid CPh3+ cation is used for abstracting the methyl group from the metal center. B(C6F5)4xe2x88x92 likewise functions as a weakly coordinating anion.
Industrial utilization of metallocene catalysts requires the catalyst system to be made heterogeneous in order to achieve an appropriate morphology of the resulting polymer. The application of cationic metallocene catalysts based on the abovementioned borate anions to a support is described in WO-91/09882. Here, the catalyst system is formed by applying a dialkylmetallocene compound and a Brxc3x6nsted acid, quaternary ammonium compound containing a non-coordinating anion such as tetrakispentafluorophenylborate to an inorganic support. The support material is modified beforehand by means of a trialkylaluminum compound. A disadvantage of this method of applying the catalyst to a support is that only a small proportion of the metallocene used is fixed to the support material by physisorption. When the catalyst system is metered into the reactor, the metallocene can easily become detached from the support surface. This leads to a partially homogeneous polymerization which results in an unsatisfactory polymer morphology.
WO-96/04319 describes a catalyst system in which the cocatalyst is covalently bound to the support material. However, this catalyst system has a low polymerization activity and, in addition, the high sensitivity of the supported cationic metallocene catalysts can lead to problems in introducing them into the polymerization system.
It would therefore be desirable to develop a catalyst system which may either be activated before introduction into the reactor or be activated only in the polymerization autoclave.
It is therefore an object of the invention to provide a catalyst system which avoids the disadvantages of the prior art and nevertheless guarantees high polymerization activities and a good polymer morphology. A further object of the invention is to develop a process for preparing this catalyst system, which process makes it possible for the activation of the catalyst system to be carried out either before introduction into the reactor or else only after it has been introduced into the polymerization autoclave.
The present invention provides a supported catalyst system and provides for its use in the polymerization of olefins.
The catalyst system of the invention comprises
a) at least one metallocene,
b) at least one Lewis base of the formula I,
M2R3R4R5xe2x80x83xe2x80x83(I)
xe2x80x83where
R3, R4 and R5 are identical or different and are each a hydrogen atom, a C1-C20-alkyl group, C1-C20-haloalkyl group, C6-C40-aryl group, C6-C40-haloaryl group, C7-C40-alkylaryl group or C7-C40-arylalkyl group, where two radicals or all three radicals R3, R4 and R5 may be connected to one another via C2-C20-units, and
M2 is an element of main group V of the Periodic Table of the Elements,
c) a support,
d) at least one organoboroaluminum compound which is built up of units of the formula II
Ri1M3xe2x80x94Oxe2x80x94M3Rj2xe2x80x83xe2x80x83(II)
xe2x80x83where
R1 and R2 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C40-group, in particular C1-C20-alkyl, C1-C20-haloalkyl, C1-C10-alkoxy, C6-C20-aryl, C6-C20-haloaryl, C6-C20-aryloxy, C7-C40-arylalkyl, C7-C40-haloarylalkyl, C7-C40-alkylaryl or C7-C40-haloalkylaryl, or R1 is an xe2x80x94OSiR3 group, where R are identical or different and are as defined for R1,
M3 are identical or different and are each an element of main group III of the Periodic Table of the Elements and
i and j are each an integer 0, 1 or 2,
and is covalently bound to the support, and, if desired,
e) an organometallic compound of the formula V
[M4R6p]kxe2x80x83xe2x80x83(V)
xe2x80x83where
M4 is an element of main group I, II or III of the Periodic Table of the Elements,
R6 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C40-group, in particular C1-C20-alkyl, C6-C40-aryl, C7-C40-arylalkyl or C7-C40-alkylaryl,
p is an integer from 1 to 3 and
k is an integer from 1 to 4.
The Lewis bases of the formula (I) are preferably ones in which M2 is nitrogen or phosphorus. Examples of such compounds are triethylamine, triisopropylamine, triisobutylamine, tri(n-butyl)amine, N,N-dimethylaniline, N,N-diethylaniline, N,N-2,4,6-pentamethylaniline, dicyclohexylamine, pyridine, pyrazine, triphenylphosphine, tri(methylphenyl)phosphine and tri(dimethylphenyl)phosphine.
The support is a porous inorganic or organic solid. The support preferably comprises at least one inorganic oxide such as silicon oxide, aluminum oxide, aluminosilicates, zeolites, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, ThO2, Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O or
Li2O, in particular silicon oxide and/or aluminum oxide.
The support can also comprise at least one polymer, e.g. a homopolymer or copolymer, a crosslinked polymer or polymer blend. Examples of polymers are polyethylene, polypropylene, polybutene, polystyrene, divinylbenzene-crosslinked polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polyamide, polymethacrylate, polycarbonate, polyester, polyacetal or polyvinyl alcohol.
The support has a specific surface area in the range from 10 to 1000 m2/g, preferably from 150 to 500 m2/g. The mean particle size of the support is from 1 to 500 xcexcm, preferably from 5 to 350 xcexcm, particularly preferably from 10 to 200 xcexcm.
The support is preferably porous with a pore volume of from 0.5 to 4.0 ml/g of support, preferably from 1.0 to 3.5 ml/g. A porous support has a certain proportion of voids (pore volume). The pores are usually irregular in shape, frequently spherical. The pores can be interconnected by small pore openings. The pore diameter is preferably from about 2 to 50 nm. The particle shape of the porous support depends on the after-treatment and can be irregular or spherical. The particle size of the support can be set to any desired value by, for example, cryogenic milling and/or sieving.
The catalyst system of the invention comprises, as cocatalytically active chemical compound, an organoboroaluminum compound comprising units of the formula (II).
Preference is given to compounds of the formula (II) in which M3 is boron or aluminum.
The compound comprising units of the formula (II) can be in the form of a monomer or a linear, cyclic or cage-like oligomer. It is also possible for two or more chemical compounds comprising units of the formula (II) to form dimers, trimers or higher associates by means-of Lewis acid-base interactions or condensation reactions.
Preferred cocatalytically active organoboroaluminum compounds d) correspond to the formulae (III) and (IV), 
where R1 and R2 are as defined under formula (II).
Examples of cocatalytically active compounds of the formulae (III) and (IV) are 
The organometallic compounds of the formula (V) are preferably uncharged Lewis acids in which M4 is lithium, magnesium and/or aluminum, in particular aluminum. Examples of preferred organometallic compounds of the formula (V) are trimethylaluminum, triethylaluminum, triisopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprenylaluminum, dimethylaluminum monochloride, diethylalumninum monochioride, diisobutylaluminum monochloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, dimethylaluminum trimethylsiloxide, dimethylaluminum triethylsiloxide, phenylalane, pentafluorophenylalane and o-tolylalane.
The metallocene compounds present in the catalyst system of the invention can be, for example, bridged or unbridged biscyclopentadienyl complexes which are described, for example, in EP-A-0,129,368, EP-A-0,561,479, EP-A-0,545,304 and EP-A-0,576,970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes which are described, for example, in EP-A-0,416,815, multinuclear cyclopentadienyl complexes as described, for example, in EP-A-0,632,063, p-ligand-substituted tetrahydropentalenes as described, for example, in EP-A-0,659,758 or p-ligand-substituted tetrahydroindenes as described, for example, in EP-A-0,661,300.
It is also possible to use organometallic compounds in which the complexing ligand does not contain a cyclopentadienyl ligand. Examples are diamine complexes of transition groups III and IV of the Periodic Table of the Elements, as are described, for example, in D.H. McConville, et al., Macromolecules, 1996, 29, 5241 and D.H. McConville, et al., J. Am. Chem. Soc., 1996, 118, 10008. It is also possible to use diimine complexes of transition group VIII of the Periodic Table of the Elements (e.g. Ni2+ or Pd2+ complexes), as are described in Brookhart et al., J. Am. Chem. Soc., 1995, 117, 6414 and Brookhart et al., J. Am. Chem. Soc., 1996, 118, 267.
Furthermore, 2,6-bis(imino)pyridyl complexes of transition group VIII of the Periodic Table of the Elements (e.g. Co2+ or Fe2+ complexes), as are described in Brookhart et al., J. Am. Chem. Soc., 1998, 120, 4049 and Gibson et al., Chem. Commun. 1998, 849, can be used. Metallocene compounds whose complexing ligand contains heterocycles can be also be used. Examples are described in WO 98/22486.
Preferred metallocene compounds are unbridged or bridged compounds of the formula VI, 
where
M1 is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
R7 are identical or different and are each a hydrogen atom or SiR312, where R12 are identical or different and are each a hydrogen atom or a C1-C40-group such as C1-C20-alkyl, C1-C10-fluoroalkyl, C1-C10-alkoxy, C6-C20-aryl, C6-C10-fluoroaryl, C6-C10-aryloxy, C2-C10-alkenyl, C7-C40-arylalkyl, C7-C40-alkylaryl or C8-C40-arylalkenyl, or R7 are each a C1-C30-group such as C1-C25-alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C3-C15-alkylalkenyl, C6-C24-aryl, C5-C24-heteroaryl such as pyridyl, furyl or quinolyl, C7-C30-arylalkyl, C7-C30-alkylaryl, fluorine-containing C1-C25-alkyl; fluorine-containing C6-C24-aryl, fluorine-containing C7-C30-arylalkyl, fluorine-containing C7-C30-alkylaryl or C1-C12-alkoxy, or two or more radicals R7 can be connected to one another such that the radicals R7 and the atoms of the cyclopentadienyl ring which connect them form a carbocyclic or heterocyclic C4-C24-ring system which may in turn be substituted,
R8 are identical or different and are each a hydrogen atom or SiR312, where R12 are identical or different and are each a hydrogen atom or a C1-C40-group such as C1-C20-alkyl, C1-C10-fluoroalkyl, C1-C10-alkoxy, C6-C14-aryl, C6-C10-fluoroaryl, C6-C10-aryloxy, C2-C10-alkenyl, C7-C40-arylalkyl, C7-C40-alkylaryl or C8-C40-arylalkenyl, or R8 are each a C1-C30-group such as C1-C25-alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C3-C15-alkylalkenyl, C6-C24-aryl, C5-C24-heteroaryl such as pyridyl, furyl or quinolyl, C7-C30-arylalkyl, C7-C30-alkylaryl, fluorine-containing C1-C25-alkyl, fluorine-containing C6-C24-aryl, fluorine-containing C7-C30-arylalkyl, fluorine-containing C7-C30-alkylaryl or C1-C12-alkoxy, or two or more radicals R8 can be connected to one another such that the radicals R8 and the atoms of the cyclopentadienyl ring which connect them form a carbocyclic or heterocyclic C4-C24-ring system which may in turn be substituted,
l is 5 when v=0, and l is 4 when v=1,
m is 5 when v=0, and m is 4 when v=1,
L1 can be identical or different and are each a hydrogen atom, a C1-C10-hydrocarbon group such as C1-C10-alkyl or C6-C10-aryl, a halogen atom or OR9, SR9, OSiR39, SiR39, PR29 or NR29, where R9 is a halogen atom, a C1-C10 alkyl group, a halogenated C1-C10-alkyl group, a C6-C20-aryl group or a halogenated C6-C20-aryl group, or L1 are each a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
o is an integer from 1 to 4, preferably 2,
Z is a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
Examples of Z are MR10R11 groups, where M is carbon, silicon, germanium or tin and R10 and R11 are identical or different C1-C20-hydrocarbon-containing groups such as C1-C10-alkyl, C6-C14-aryl or trimethylsilyl. Z is preferably CH2, CH2CH2, CH(CH3)CH2, CH(C4H9)C(CH3)2, C(CH3)2, (CH3)2Si, (CH3)2 Ge, (CH3)2, Sn, (C6H5)2Si, (C6H5)(CH3)Si, (C6H5)2 Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, oxe2x80x94C6H4 or 2,2xe2x80x2-(C6H4)2. It is also possible for Z together with one or more radicals R7 and/or R8 to form a monocyclic or polycyclic ring system.
Preference is given to chiral, bridged metallocene compounds of the formula (VI), in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted such that they form an indenyl ring, a sulfur-, nitrogen- or oxygen-containing heterocycle analogous to indenyl or a sulfur-, nitrogen- or oxygen-containing heterocylce analagous to pentalene. 
The abovementioned rings are preferably substituted, in particular (using the numbering given in formula (VII)) in the 2, 4, 2,4, 2,4,5, 2,4,6, 2,4,7 or 2,4,5,6 positions, by C1-C20-groups such as C1-C10-alkyl or C6-C20-aryl, where two or more substituents on the rings mentioned can also together form a ring system.
Chiral, bridged metallocene compounds of the formula (VI) can be used as pure racemic or pure meso compounds. However, it is also possible to use mixtures of a racemic compound and a meso compound.
Examples of metallocene compounds are:
dimethylsilanediylbis(indenyl)zirconium dichloride
dimethylsilanediylbis(4-naphthylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methylbenzindenyl)zirconium dichloride
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-(1-naphthyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-(2-naphthyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-t-butylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-isopropylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-ethylindenyl)zirconium dichloride
dimethyisilanediylbis(2-methyl4-acenaphthindenyl)zirconium dichloride
dimethylsilanediylbis(2,4-dimethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-ethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-phenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4,6-diisopropylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4,5-diisopropylindenyl)zirconium dichloride
dimethylsilanediylbis(2,4,6-trimethylindenyl)zirconium dichloride
dimethylsilahediylbis(2,5,6-trimethylindenyl)zirconium dichloride
dimethylsilanediylbis(2,4,7-trimethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-5-isobutylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-5-t-butylindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2methyl-4-isopropylindenyl)zirconium dichioride
methyl(phenyl)silanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methyl-4,5-(methylbenz)indenyl)zirenonuiu dichloride
methyl(phenyl)silanediylbis(2-methyl-4,5-(tetramethylbenz)indenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methyl-4-acenaphthindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methylindenyl)zirconium dichloride
methyl(phenyl)silanediylbis(2-methyl-5-isobutylindenyl)zirconium dichloride
1,2-ethanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride
1,4-butanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride
1,2-ethanediylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride
1,4-butanediylbis(2-methyl-4-isopropylindenyl)zirconium dichloride
1,4-butanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride
1,2-ethanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride
1,2-ethanediylbis(2,4,7-trimethylindenyl)zirconium dichloride
1,2-ethanediylbis(2-methylindenyl)zirconium dichloride
1,4-butanediylbis(2-methylindenyl)zirconium dichloride
[4-(xcex75-cyclopentadienyl)4,6,6-trimethyl(xcex75-4,5-tetrahydropentalene)]-dichlorozirconium
[4-(xcex75-3xe2x80x2-trimethylsilylcyclopentadienyl)-4,6,6-trimethyl(xcex75-4,5-tetrahydropentalene)]-dichlorozirconium
(4-(xcex75-3xe2x80x2-isopropylcyclopentadienyl)-4,6,6-trimethyl(xcex75-4,5-tetrahydropentalene)]-dichlorozirconium
[4-(xcex75-cyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorotitanium
[4-(xcex75-cyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]-dichlorozirconium
[4-(xcex75-cyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]-dichlorohafnium
[4-(xcex75-3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorotitanium
4-(xcex75-3-isopropylcyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorotitanium
4-(xcex75-3-methylcyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorotitanium
4-(xcex75-3-trimethysilylcyclopentadienyl)-2-trimethylsilyl-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorotitanium
4-(xcex75-3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(xcex75-4,5,6,7-tetrahydroindenyl)]dichlorozirconium
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilyidichlorotitanium
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyidichlorotitanium
(methylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilyidichlorotitanium
(methylamido)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyldichlorotitanium
(tert-butylamido)(2,4-dimethyl-2,4-pentadien-1-yl)dimethylsilyidichlorotitanium
bis(cyclopentadienyl)zirconium dichloride
bis(n-butylcyclopentadienyl)zirconium dichloride
bis(1,3-dimethylcyclopentadienyl)zirconium dichloride
tetrachloro[1-[bis(xcex75-1H-inden-1-ylidene)methylsilyl]-3-xcex75-cyclopenta-2,4-dien-1-ylidene)-3-xcex75-9H-fluoren-9-ylidene)butane]dizirconium
tetrachloro[2-[bis(xcex75-2-methyl-1H-inden-1-ylidene)methoxysilyl]-5-xcex75-2,3,4,5-tetramethylcyclopenta-2,4-dien-1-ylidene)-5-(xcex75-9H-fluoren-9-ylidene)hexane]dizirconium
tetrachloro[1-(bis(xcex75-1H-inden-1-ylidene)methylsilyl]-6-(xcex75-cyclopenta-2,4-dien-1-ylidene)-6-(xcex75-9H-fluoren-9-ylidene)-3-oxaheptane]dizirconium
dimethylsilanediyibis(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trifuoromethylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methoxyphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-trifuoromethylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-methoxyphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)dimethyl-zirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trifluoromethylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methoxyphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-tert-butylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-methylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-ethylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-trifluoromethylphenylindenyl)dimethylzirconium
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-methoxyphenylindenyl)dimethyizirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)dimethyizirconium
dimethylsilanediylbis(2-ethyl4-(4xe2x80x2-trimethylsilyiphenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)hafnium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)titanium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-methylphenyl)indenyl)zircnium dichloride
dimethylsilanediylbis(2methyl-4-(4xe2x80x2-n-propylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2methyl-4-(4xe2x80x2-n-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-hexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-n-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-metylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-ethylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-n tylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-hexyiphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-exylpheny)indenyl)zirconium dichloride
dimethyisilanediyibis(2-ethyl-4-(4xe2x80x2-entylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-cyclohexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-sec-butylphenyl)indenyl)zirconium dichioride
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-phenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-methylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-ethylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-iso-propylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-n-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-hexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-cyclohexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-sec-butphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-propyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-phenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-methylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-ethylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-n-propylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-isopropylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-n-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-hexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-cyclohexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-sec-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-n-butyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-phenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-methylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-ethylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-n-propylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-isopropylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-n-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediyibis(2-hexyl-4-(4xe2x80x2-hexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-cyclohexylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-sec-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-hexyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium bis(dimethylamide)
dimethylsilanediylbis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dibenzylzirconium
dimethylsilanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dimethylzirconium
dimethylgermanediylbis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylgermanediylbis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)hafnium dichloride
dimethylgermanediylbis(2-propyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)titanium dichloride
dimethylgermanediylbis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
ethylidenebis(2-ethyl-4-phenyl)indenyl)zirconium dichloride
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
ethylidenebis(2-n-propyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
ethylidenebis(2-n-butyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)titanium dichloride
ethylidenebis(2-hexyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dibenzylzirconium
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dibenzylhafnium
ethylidenebis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dibenzyltitanium
ethylidenebis(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)dimethylhafnium
ethylidenebis(2-n-propyl-4-phenyl)indenyl)dimethyltitanium
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium bis(dimethylamide)
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)hafnium bis(dimethylamide)
ethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)titanium bis(dimethylamide)
methylethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
methylethylidenebis(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)hafnium dichloride
phenylphosphinediyl(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
phenylphosphinediyl(2-methyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
phenylphosphinediyl(2-ethyl-4-(4xe2x80x2-tert-butylphenyl)indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsitanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentaiene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methy-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-ethyl-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-ethylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-propyphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichioride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-propylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-pheny(-4-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethyisilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediy(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-isopropylpheny(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-isopropylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentatene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-butylpheny(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentatene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-s-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methy4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-oxapentalene)(2-methyl-4-(4xe2x80x2-n-pentylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-n-hexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyi4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-cyclohexylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-trimethysilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4,4hiapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl 4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-trimethylsilylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-adamantylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-tris(trifluoromethyl)methylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-ethyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5,6-dihydr-4-azapentalene)(2-ethyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-ethyl-4-(4xe2x80x2-tert-butylphenyltetrahydroindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-n-butyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
ethylidene(2-methyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-trimethylsilyl4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-tolyl-5-azapentalene)(2-n-propyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylgermyldiyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
methylethylidene(2,5-dimethyl-4-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-diisopropyl-6-azapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2,6-dimethyl-4-(4xe2x80x2-tertbutylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(6xe2x80x2-tert-butylnaphthylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-(6xe2x80x2-tert-butylanthracenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-phosphapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
diphenylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
methylphenylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
methylidene(2,5-dimethyl-4-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylmethylidene(2,5-dimethyl-6-thiapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
diphenylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
diphenylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-(4xe2x80x2-tert-butylphenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5thiapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(indenyl)zirconium dichioride
dimethylsilanediyl(2-methyl-4-oxapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(indenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2methyl4peyindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2methyl4peyindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2methyl4peyindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichioride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichioride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-oxapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-oxapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-oxapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-oxapentalene)(2-methyl-4-phenylindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-4-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-5-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-N-phenyl-6-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-4-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichioride
dimethylsilanediyl(2,5-dimethyl-N-phenyl-6-azapentalene)(2-methyl-4,5-benzindenyl)zirconium dichioride
dimethylsilanediyl(2-methyl-4-thiapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-5-thiapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-6-thiapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4-thiapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6-thiapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2-methyl-4-oxapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethyisilanediyl(2-methyl-5-oxapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-4oxapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediyl(2,5-dimethyl-6oxapentalene)(2-methyl-4,5-benzindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-azapentalene)zirconium dichloride
dimethylsilanediylbis(2-methyl-5-azapentalene)zirconium dichloride
dimethylsila ned iylbis(2-methyl-6-azapentalene:)zirconium dichloride
dimethylsilanediylbis(2-methyl-N-phenyl-4-azapentalene)zirconium dichloride
dimethylsilanediyibis(2-methyl-N-phenyl-5-azapentalenie)zirconium dichloride
dimethylsilanediylbis(2-methyl-N-phenyl-6-azapentalene)zirconium dichloride
dimethylsilanediylbis(2,5-dimethyl-4-azapentalene)zirconium dichlonde
dimethylsilanediylbis(2,5-dimethyl-6-azapentalehe)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-thiapentalene)zirconium dichloride
dimethylsilanediyibis(2-methyl-4thiapentalene)zirconium dichloride
dimethylsilanediylbis(2-methyl-6-thiapentalene)zirconium dichloride
dimethylsilanediylbis(2,5-dimethyl-4-thiapentalene)zirconium dichloride
dimethylsilanediylbis(2,5-dimethyl-6-thiapentalene)zirconium dichloride
dimethylsilanediylbis(2-methyl-4-oxapentalene)zirconium dichloride
dimethylsilanediylbis(2-methyl-5-oxapentalene)zirconium dichloride
dimethylsilanediylbis(2-methyl-6-oxapentalene)zirconium dichloride
dimethylsilanediylbis(2,5-dimethyl-4-oxapentalene)zirconium dichloride
dimethylsilanediylbis(2,5-dimethyl-6-oxapentalene)zirconium dichloride
The catalyst system of the invention can be obtained by reacting a Lewis base of the formula (I) and an organoboroaluminum compound which is built up of units of the formula (II) with a support. This is followed by reaction with a solution or suspension of one or more metallocene compounds of the formula (VI) and, if desired, one or more organometallic compounds of the formula (V).
The activation of the catalyst system can thereby be carried out either before introduction into the reactor or only after introduction into the reactor. Furthermore, a process for preparing polyolefins is also described. The addition of a further chemical compound which is added as additive before the polymerization can additionally be advantageous.
To prepare the catalyst system of the invention, the support material is suspended in an organic solvent. Suitable solvents are aromatic or aliphatic solvents such as hexane, heptane, toluene or xylene or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene. The support can be pretreated beforehand with a compound of the formula (V). Subsequently, one or more compounds of the formula (I) are added to this suspension; the reaction time can be from 1 minute to 48 hours, preferably from 10 minutes to 2 hours. The reaction solution can be isolated and subsequently resuspended or else can be reacted directly with a cocatalytically active organoboroaluminum compound which is built up of units of the formula (II). The reaction time here is from 1 minute to 48 hours, with a reaction time of from 10 minutes to 2 hours being preferred. Preference is given to reacting from 1 to 4 equivalents of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound which is built up of units of the formula (II). Particular preference is given to reacting one equivalent of a Lewis base of the formula (I) with one equivalent of a cocatalytically active compound built up of units of the formula (II). The product of this reaction is a compound capable of forming metallocenium ions which is covalently fixed to the support material. It is hereinafter referred to as modified support material. The reaction mixture is subsequently filtered and washed with one of the abovementioned solvents. The modified support material is then dried in a high vacuum. After drying, the modified support material can be resuspended and after-treated with a compound of the formula (V). However, the compound of the formula (V) can also be added prior to filtration and drying of the modified support material. The application of one or more metallocene compounds, preferably of the formula (VI), and one or more organometallic compounds of the formula (V) to the modified support material is preferably carried out by dissolving or suspending one or more metallocene compounds of the formula (VI) in an above-described solvent and subsequently reacting it/them with one or more compounds of the formula (V), which is/are preferably likewise dissolved or suspended. The stoichlometric ratio of metallocene compound of the formula (VI) and organometallic compound of the formula (V) is from 100:1 to 10xe2x88x924:1. The ratio is preferably from 1:1 to 10xe2x88x922:1.
The modified support material together with one of the abovementioned solvents can either be placed directly in the polymerization reactor or in a reaction flask. The mixture of metallocene compound of the formula (VI) and organometallic compound of the formula (V) is then added. As an alternative, one or more metallocene compounds of the formula (VI) can be added to the modified support material without prior addition of an organometallic compound of the formula (V). The ratio of modified support to metallocene compound of the formula (VI) is preferably from 10 g:1 xcexcmol to 10xe2x88x922 g:1 xcexcmol. The stoichlometric ratio of metallocene compound of the formula (VI) to the supported, cocatalytically active organoboroaluminum compound comprising units of the formula (II) is from 100:1 to 10xe2x88x924:1, preferably from 1:1 to 10xe2x88x922:1.
The supported catalyst system can be used directly for the polymerization. However, it is also possible for the solvent to be removed and the catalyst system to be subsequently resuspended and used for the polymerization. The advantage of this activation method is that it offers the option of allowing the polymerization-active catalyst system to be formed only in the reactor. This prevents decomposition from occurring when introducing the air-sensitive catalyst in to the reactor.
Furthermore, a process for preparing an olefin polymer in the presence of the catalyst system of the invention is also described. The polymerization can be a homopolymerization or a copolymerization.
Preference is given to polymerizing olefins of the formula Rxcex1(xe2x80x94CHxe2x95x90CHxe2x80x94Rxcex2, where Rxcex1 and Rxcex2 are identical or different and are each a hydrogen atom, a halogen atom, an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxyl or carboxylic ester group or a saturated or unsaturated hydrocarbon radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, which may be substituted by an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxyl or carboxylic ester group, or Rxcex1 and Rxcex2 together with the atoms connecting them form one or more rings. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbornene vinylnorbornene, tetracyclododecene, ethylidenenorbornene, dienes such as 1,3-butadiene or 1,4-hexadiene, biscyclopentadiene or methyl methacrylate.
Particular preference is given to homopolymerizing propylene or ethylene, copolymerizing ethylene with one or more C3-C20-1-olefins, in particular propylene, and/or one or more C4-C20-dienes, in particular 1,3-butadiene, or copolymerizing norbornene and ethylene.
The polymerization is preferably carried out at a temperature of from xe2x88x9260 to 300xc2x0 C., particularly preferably from 30 to 250xc2x0 C. The pressure is from 0.5 to 2500 bar, preferably from 2 to 1500 bar. The polymerization can be carried out continuously or batchwise, in one or more stages, in solution, in suspension, in the gas phase or in a supercritical medium.
The supported catalyst system can either be formed directly in the polymerization system or can, as powder or while still moist with solvent, be resuspended and metered as suspension in an inert suspension medium into the polymerization system.
A prepolymerization can be carried out by means of the catalyst system of the invention. For the prepolymerization, preference is given to using the (or one of the) olefin(s) used in the polymerization.
To prepare olefin polymers having a broad molecular weight distribution, preference is given to using catalyst systems comprising two or more different transition metal compounds, e.g. metallocenes.
To remove catalyst poisons present in the olefin, purification using an aluminum alkyl, for example trimethylaluminum, triethylaluminum or triisobutylaluminum, is advantageous. This purification can be carried out either in the polymerization system itself or the olefin is brought into contact with the Al compound prior to addition to the polymerization system and is subsequently separated off again.
If necessary, hydrogen is added as molecular weight regulator and/or to increase the activity. The total pressure in the polymerization system is from 0.5 to 2500 bar, preferably from 2 to 1500 bar.
The compound described in the invention is employed in a concentration, based on the transition metal, of preferably from 1031 3 to 10xe2x88x928, preferably from 10xe2x88x924 to 10xe2x88x927 mol, of transition metal per dim3 of solvent or per dim3 of reactor volume.
Suitable solvents for preparing both the supported chemical compound of the invention and the catalyst system of the invention are aliphatic or aromatic solvents such as hexane or toluene, ether solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
Before addition of the catalyst system of the invention or before activation of the catalyst system of the invention in the polymerization system, it is possible for an alkylaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum to be introduced into the reactor to make the polymerization system inert (for example to remove catalyst poisons present in the olefin). This is added to the polymerization system in a concentration of from 200 to 0.001 mmol of Al per kg of reactor contents. Preference is given to using triisobutylaluminum or triethylaluminum in a concentration of from 10 to 0.01 mmol of Al per kg of reactor contents; this enables a small Al/M1 molar ratio to be employed in the synthesis of a supported catalyst system. In addition, an additive such as an antistatic can be used in the process of the invention, e.g. for improving the particle morphology of the olefin polymer. In general, it is possible to use all antistatics which are suitable for the polymerization. Examples are salt mixtures of calcium salts of Medialan and chromium salts of N-stearylanthranilic acid, which are described in DE-A-3,543,360. Further suitable antistatics are, for example, C12-C22- fatty acid soaps of alkali metals or alkaline earth metals, salts of sulfonic acid esters, esters of polyethylene glycols and fatty acids, polyoxyethylene alkyl ethers, etc. An overview of antistatics is given in EP-A-0,107,127.
The antistatic used can also be a mixture of a metal salt of Medialan, a metal salt of anthranilic acid and a polyamine, as described in EP-A-0,636,636.
Commercially available products such as Stadis(copyright) 450 from DuPont, a mixture of toluene, isopropanol, dodecylbenzenesulfonic acid, a polyamine, a copolymer of 1-decene and SO2 and also 1-decene or ASA(copyright) -3 from Shell and ARU5R(copyright) 163 from ICI can likewise be used.
The antistatic is preferably used as a solution; in the preferred case of Stadis(copyright) 450, preference is given to using from 1 to 50% by weight of this solution, more preferably from 5 to 25% by weight, based on the mass of the supported catalyst used (support together with covalently fixed metallocenium-forming compound and one or more metallocene compounds, e.g. of the formula VI). However, the required amounts of antistatic can vary within a wide range, depending on the type of antistatic used. The actual polymerization is preferably carried out in liquid monomers (bulk) or in the gas phase.
The antistatic can be added to the polymerization at any point in time. For example, a preferred procedure is to resuspend the supported catalyst system in an organic solvent, preferably an alkane such as heptane or isododecane. It is subsequently introduced into the polymerization autoclave while stirring. The antistatic is then added. The polymerization is carried out at temperatures in the range from 0 to 100xc2x0 C. A further preferred procedure is to add the antistatic to the polymerization autoclave before addition of the supported catalyst system. Subsequently, the resuspended supported catalyst system is introduced while stirring at temperatures in the range from 0 to 100xc2x0 C. The polymerization time can be in the range from 0.1 to 24 hours. Preference is given to a polymerization time in the range from 0.1 to 5 hours.
In the above-described process, no deposits on the reactor occur, no agglomerates are formed and the productivity of the catalyst system used is high. The polymers prepared using the process of the invention have a narrow molecular weight distribution and a good particle morphology.
The following examples serve to illustrate the invention.
General information: Preparation and handling of the compounds were carried out with exclusion of air and moisture under argon (Schlenk technique). All solvents required were dried before use by boiling for a number of hours over suitable desiccants and subsequent distillation under argon.